CN114907892A - Deoxidation method and deoxidation system for low-concentration coal bed gas - Google Patents
Deoxidation method and deoxidation system for low-concentration coal bed gas Download PDFInfo
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- CN114907892A CN114907892A CN202110176687.4A CN202110176687A CN114907892A CN 114907892 A CN114907892 A CN 114907892A CN 202110176687 A CN202110176687 A CN 202110176687A CN 114907892 A CN114907892 A CN 114907892A
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- 239000003245 coal Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000007789 gas Substances 0.000 claims abstract description 128
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000463 material Substances 0.000 claims abstract description 64
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000001301 oxygen Substances 0.000 claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 54
- 238000005406 washing Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 239000000498 cooling water Substances 0.000 claims description 22
- 239000000571 coke Substances 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 9
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003830 anthracite Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000004880 explosion Methods 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000011261 inert gas Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Abstract
The invention relates to a deoxidation method before comprehensive utilization of coal bed gas, and provides a deoxidation method of low-concentration coal bed gas, which comprises the following steps: (1) contacting the coal bed gas with hot water to obtain a material I; based on volume content, the coal bed methane content is 5-16%, and the oxygen content is 14-20%; based on volume content, the oxygen content of the material I is less than or equal to 12%, and/or the methane content is less than or equal to 4%; (2) performing deoxidation reaction on the material I and a carbon material to obtain a material II; based on the volume content, the oxygen content of the material II is less than or equal to 0.5 percent; (3) and cooling the material II to 130-250 ℃, washing and dedusting, and cooling to 50-85 ℃ to obtain the deoxidized coal bed gas. The method can efficiently and safely remove the oxygen in the coal bed gas with the methane volume content within the explosion limit range.
Description
Technical Field
The invention relates to a deoxidation method before comprehensive utilization of coal bed gas, in particular to a deoxidation method and a deoxidation system for low-concentration coal bed gas.
Background
Coal bed gas is commonly called coal mine gas, coal bed gas with methane concentration of more than 30% can be generally used for direct combustion and utilization, and coal bed gas with methane concentration of less than 30% can be generally used after being concentrated. At present, the coal bed gas separation and purification technology mainly comprises three types of low-temperature cryogenic separation, pressure swing adsorption, membrane separation and the like. The explosion limit of methane in air is 4.9% -16%, and the explosion limit is widened by pressurizing operation. If the low-concentration oxygen-containing coal bed gas is directly enriched and concentrated, the concentration is carried out along with CH 4 Increasing concentration and O 2 The concentration rises continuously, and inevitably, a stage is just in the methane explosion range, so that a great safety risk exists. Therefore, the coal bed gas deoxidation technology has become one of the key technologies for coal bed gas utilization.
Currently, catalytic combustion and coke combustion are the main methods for deoxidizing coal bed gas. The catalytic combustion method is to remove oxygen by burning methane in the coal bed gas, and the coke combustion method is mainly to remove oxygen by burning coke and oxygen in the coal bed gas.
CN1919986A discloses a coalbed methane coke deoxidation process, which is to deoxidize coalbed methane through a hot coke layer or a smokeless coalbed in a deoxidation reactor under normal pressure, control the deoxidation reaction temperature at 600-1000 ℃, and then perform waste heat recovery-dust removal-cooling treatment; in the deoxidation process, the oxygen content of the reaction gas entering the deoxidation reactor is adjusted to 5-9% by circulating part of the deoxidized and cooled coal bed gas into the coal bed gas before deoxidation, so that the reaction temperature can be better controlled, the methane cracking is reduced to the maximum extent, the loss of methane is ensured to be below 5%, and the possibility of explosion in the deoxidation process is reduced.
CN104629842B discloses a fixed bed coal bed gas deoxidation method and a device thereof. A fixed bed coal bed gas non-catalytic deoxidation device is provided for carrying out deoxidation on the coal bed gas with the methane content of more than 28% and less than or equal to 50%. The fixed bed reactor is used as a main device for deoxidizing the coal bed gas, the coal bed gas is deoxidized through a glowing fuel layer in the fixed bed, the temperature of the deoxidation reaction is controlled to be 500 plus 700 ℃ by adjusting the water flow in a water jacket outside the reactor, so that the oxygen content in the coal bed gas is reduced to be less than 0.5 percent, the methane cracking is reduced to the maximum extent, and the loss of the methane is reduced to be less than 5 percent.
CN1919986A, the process adjusts the oxygen content of the coal bed gas entering the deoxidation reactor by adopting partial deoxidation coal bed gas circulation to control the reaction temperature, the control means is single, and the temperature is difficult to control; the highest reaction temperature is controlled to be 1000 ℃, and the methane is easy to generate cracking and oxidation reactions and is lost at the temperature; the use of partially deoxygenated coal bed gas recycle can cause secondary cracking and oxidation, further increasing methane loss.
CN104629842B, aiming at the coal bed gas with the volume percentage content of more than 28 percent and less than or equal to 50 percent to remove oxygen, the coal bed gas in the explosion limit range of 4.9-16 percent can not be processed; the deoxygenation reactor has limited heat exchange area and the center of deoxygenated fuel bed is far away from the jacket, and this results in difficult temperature control and easy temperature runaway.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for deoxidizing low-concentration coal bed gas, which can efficiently and safely remove oxygen in the coal bed gas with methane volume content in an explosion limit range.
In order to achieve the above object, in one aspect, the present invention provides a method for deoxidizing low-concentration coal bed gas, the method including:
(1) contacting the coal bed gas with hot water to obtain a material I; based on the volume content, the content of the coal bed methane is 5-16%, and the content of the oxygen is 14-20%; the oxygen content of the material I is less than or equal to 12%, and/or the methane content is less than or equal to 4%;
(2) performing deoxidation reaction on the material I and a carbon material to obtain a material II; the deoxidation reaction temperature is 500-700 ℃; the oxygen content of the material II is less than or equal to 0.5 percent;
(3) cooling the material II to 130-250 ℃, washing and dedusting, and then cooling to 50-85 ℃ to obtain deoxidized coal bed gas; wherein, the gas content is based on the volume content.
Preferably, in step (1), the coal bed gas pressure is 3-10kPa (gauge pressure).
Preferably, the temperature of the hot water is 50-85 ℃.
Preferably, in the step (2), the deoxidation reaction conditions include: the temperature is 525 ℃ plus 700 ℃, and the space velocity is 1000h plus 3000h -1 (ii) a The carbon material is at least one of semi-coking coal, anthracite, coke and biochar.
Preferably, the carbon material particle size is 3-5 mm.
In a second aspect, the present invention provides a low concentration coalbed methane deoxidation method, which is carried out in a system comprising a saturation tower, a tubular reactor, a steam drum, a cooler and a washing tower, and comprises the following steps:
a. the coal bed gas is in countercurrent contact with hot water in a saturation tower to obtain a material I; based on volume content, the coal bed methane content is 5-16%, and the oxygen content is 14-20%; the oxygen content of the material I is less than or equal to 12%, and/or the methane content is less than or equal to 4%;
b. feeding the material I into a tubular reactor, and carrying out deoxidation reaction on the material I and a carbon material to obtain a material II; the deoxidation reaction temperature is 500-700 ℃; the oxygen content of the material II is less than or equal to 0.5 percent;
c. and cooling the material II to the temperature of 130-250 ℃ in a cooler, washing and dedusting in a washing tower, and cooling to the temperature of 50-80 ℃ to obtain the deoxidized coal bed gas.
Preferably, in the step a, the coal bed gas pressure is 3-10kPa (gauge pressure), and the hot water temperature is 50-85 ℃.
Preferably, in the step b, the deoxidation reaction conditions of the material I and the carbon material in the tubular reactor 2 comprise: the temperature is 525 ℃ plus 700 ℃, and the gas space velocity is 1000h plus 3000h -1 。
Preferably, the carbon material is at least one of semi-coke coal, anthracite, semi-coke, and biochar.
Preferably, the boiler water through the cooler controls the reaction temperature of the shell and tube reactor.
Preferably, the boiler water temperature is 45-55 ℃.
Preferably, the washing tower carries out washing and dust removal by adopting cooling water and/or supplementary cooling water at the bottom of the saturation tower to be in countercurrent contact with the material II from the cooler; the temperature of the cooling water and/or the supplementary cooling water at the bottom of the saturation tower is 25-35 ℃.
In a third aspect, the present invention provides a low-concentration coalbed methane deoxidation system, which comprises: a saturation tower, a tubular reactor, a steam drum, a cooler and a washing tower;
the saturation tower is used for enabling coal bed gas to be in countercurrent contact with hot water in the saturation tower to obtain a material I;
wherein the tubular reactor is used for deoxidizing the material I and the carbon material in the tubular reactor to obtain a material II;
wherein the cooler is used for cooling the material II in the cooler;
wherein the washing tower is used for washing and dedusting the cooled materials to obtain the deoxidized coal bed gas;
and cold water and/or supplementary cooling water discharged from the bottom of the saturated tower are/is sent to a washing tower to be used as cooling water, and hot water discharged from the bottom of the washing tower is sent to the saturated tower to be used as spray water.
The cooler is connected with the column reactor through a pipeline, so that the boiler water in the cooler can be conveyed to the column reactor, and the temperature of the column reactor is controlled through the boiler water.
The boiler water of the tubular reactor is gasified, the generated steam is sent to a steam drum, after steam-water separation of the steam drum, steam and saturated water are obtained, and the saturated water is sent back to the tubular reactor.
The deoxidation method of the low-concentration coal bed gas provided by the invention can efficiently remove the oxygen in the coal bed gas with the methane volume content within the explosion limit range, so that the oxygen volume content in the coal bed gas is reduced to be below 0.5%.
According to the deoxidation method of the low-concentration coal bed gas, provided by the invention, the phase change is forced to carry out fluidized heat exchange outside the tubular reactor, so that the deoxidation reaction temperature is effectively controlled, and the methane loss in the deoxidation process of the coal bed gas is less than 5%.
According to the deoxidation method of the low-concentration coal bed gas, provided by the invention, the hot water is used for carrying out water vapor saturation on the coal bed gas, so that the methane concentration in the coal bed gas before deoxidation is separated from the explosion limit of 5-16% or more than 12% of oxygen content, and the safety of the deoxidation process is ensured.
Drawings
FIG. 1 is a schematic diagram of a low-concentration coalbed methane deoxidation system and a coalbed methane deoxidation method.
Description of the reference numerals
1-saturation tower
2-tubular reactor
3-steam pocket
4-cooler
5-washing tower
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a deoxidation method of low-concentration coal bed gas, which comprises the following steps:
(1) contacting the coal bed gas with hot water to obtain a material I; the content of the coal bed methane is 5-16%, and the content of the oxygen is 14-20%; the oxygen content of the material I is less than or equal to 12 percent, and/or the methane content is less than or equal to 4 percent;
(2) deoxidizing the material I and a carbon material to obtain a material II; the deoxidation reaction temperature is 500-700 ℃; the oxygen content of the material II is less than or equal to 0.5 percent;
(3) cooling the material II to the temperature of 130-250 ℃, washing and dedusting, and cooling to the temperature of 50-80 ℃ to obtain deoxidized coal bed gas; wherein, the gas content is based on the volume content.
According to the invention, the method is applied to deoxidation of the coal bed gas in an explosion limit range, the coal bed gas is contacted with hot water, the water content in the coal bed gas is increased to obtain a material I, and the oxygen content of the material I is reduced to be below 12% and/or the methane content is reduced to be below 4%. The gas concentration of the material I is out of the explosion range, and the possibility of explosion in the deoxidation process is reduced.
According to the invention, in the step (1), preferably, the temperature of the hot water is 50-85 ℃, and in the temperature range, the coal bed gas has a good humidifying effect, and the oxygen content and the methane content in the coal bed gas can be effectively reduced.
According to the invention, in the step (2), preferably, the temperature for deoxidizing the material I and the carbon material is 500-700 ℃, more preferably 525-700 ℃. In the reaction temperature, the oxygen of the coal bed gas can be effectively removed, and the loss of methane is low.
According to the present invention, the carbon material is selected from a wide range, and preferably, the carbon material is at least one of semi-coke coal, anthracite, semi-coke, and biochar.
According to the present invention, it is preferable that the carbon material has a particle size of 3 to 5 mm.
The invention provides a low-concentration coal bed gas deoxidation method, which is carried out in a system comprising a saturation tower 1, a tubular reactor 2, a steam drum 3, a cooler 4 and a washing tower 5, and comprises the following steps:
a. the coal bed gas is in countercurrent contact with hot water in a saturation tower 1 to obtain a material I; based on volume content, the coal bed methane content is 5-16%, and the oxygen content is 14-20%; the oxygen content of the material I is less than or equal to 12 percent, and/or the methane content is less than or equal to 4 percent;
b. the material I enters a tubular reactor 2 and is subjected to deoxidation reaction with a carbon material to obtain a material II; the deoxidation reaction temperature is 500-700 ℃; the oxygen content of the material II is less than or equal to 0.5 percent;
the boiler water of the tubular reactor 2 is gasified, the generated steam is sent to the steam drum 3, after the steam-water separation of the steam drum 3, steam and saturated water are obtained, and the saturated water is sent back to the tubular reactor 2;
c. and cooling the material II to the temperature of 130-250 ℃ in a cooler 4, washing and dedusting in a washing tower 5, and cooling to the temperature of 50-80 ℃ to obtain the deoxidized coal bed gas.
According to the invention, in step a, the coal bed gas pressure is preferably 3-10kPa (gauge).
According to the invention, in the step a, the temperature of the hot water in the saturation tower 1 is preferably 50-85 ℃.
According to the invention, the preferable reaction conditions are adopted, the coal bed gas humidification effect is good, and the oxygen content and the methane content in the coal bed gas can be effectively reduced.
According to the present invention, in step b, preferably, the deoxidation reaction conditions of the material i with the carbon material in the tubular reactor 2 include: the temperature is 525 ℃ and 700 ℃, and the temperature is 1000h and 3000h -1 (ii) a Within the range of the deoxidation condition, the oxygen of the coal bed gas can be effectively removed, and the loss of methane is low.
According to the present invention, the carbon material is selected from a wide range, and preferably, the carbon material is at least one of semi-coke coal, anthracite, semi-coke, and biochar.
According to the invention, the heat generated by the deoxidation reaction of the hot tubular reactor 2 is preferably removed in time through the boiler water of the cooler 4, so as to achieve the purpose of controlling the temperature, and the reaction temperature of the tubular reactor 2 is preferably controlled to be 500-700 ℃, more preferably 525-700 ℃; in the temperature range, the loss caused by cracking or burning of methane due to temperature runaway of a bed layer is avoided.
According to the invention, the boiler water is gasified in the thermal shell-and-tube reactor 2, preferably with a resulting saturated steam pressure of 0.26-0.9MPa and a temperature of 140-.
According to one embodiment of the invention, the steam is sent into the steam drum 3, after the steam-water separation of the steam drum 3, the steam is sent out, and the saturated water is sent back to the boiler water inlet of the deoxygenation reactor 2. By adopting the implementation method, waste heat is recovered, and the consumption of cooling water is saved.
According to one embodiment of the invention, the material II is cooled to 130 ℃ and 250 ℃ by the cooler 4, preferably boiler water is used as cooling medium.
According to one embodiment of the invention, the boiler water is preheated to 45-55 ℃.
According to one embodiment of the invention, the washing tower 5 carries out washing and dedusting by adopting cooling water and/or supplementary cooling water at the bottom of the saturation tower 1 to be in countercurrent contact with the material II from the cooler 4; the temperature of the cooling water and/or the supplementary cooling water at the bottom of the saturation tower 1 is 25-35 ℃. By adopting the implementation method, waste heat is recovered, and the consumption of cooling water is saved.
In a third aspect, the present invention provides a low-concentration coalbed methane deoxidation system, which comprises: a saturation tower 1, a tubular reactor 2, a steam drum 3, a cooler 4, a washing tower 5 and connecting pipelines.
According to one embodiment of the invention, cold water and/or supplementary cooling water discharged from the bottom of the saturation tower 1 are/is sent to the washing tower 5 as cooling water, and hot water discharged from the bottom of the washing tower 5 is sent to the saturation tower 1 as spray water.
According to an embodiment of the present invention, the cooler 4 is connected to the shell and tube reactor 2 by a pipe, so that the boiler water in the cooler 4 can be transferred to the shell and tube reactor 2, and the temperature of the shell and tube reactor 2 is controlled by the boiler water. By adopting the implementation method, the waste heat is recovered, and the consumption of cooling water is saved.
According to one embodiment of the invention, the boiler water of the tubular reactor 2 is gasified, the generated steam is sent to the steam drum 3, after steam-water separation of the steam drum 3, steam and saturated water are obtained, and the saturated water is sent back to the tubular reactor 2. By adopting the implementation method, the waste heat is recovered, and the consumption of cooling water is saved.
The present invention will be described in detail below by way of examples.
Example 1
a. The raw material gas composition (volume) is as follows: 5.21% of methane, 74.01% of nitrogen, 19.86% of oxygen and 0.92% of inert gas, wherein the pressure is 5kPa (gauge pressure), the raw material gas enters the saturation tower 1, the water temperature of the raw material gas enters the saturation tower 1 is 70 ℃, and the composition (volume) of the gas at the outlet of the saturation tower 1 is as follows: 3.99% of methane, 56.68% of nitrogen, 15.21% of oxygen, 23.44% of water vapor and 0.68% of inert gas;
b. the gas at the outlet of the saturation tower 1 enters a tubular reactor 2, and the space velocity in the tubular reactor 2 is 3000h -1 The bed temperature of the reactor is 510 ℃, and the semi-coke granularity is 3-5 mm;
c. gas at the outlet of the tubular reactor 2 enters a cooler 4, is cooled to 150 ℃, and then is introduced into a washing tower 5 and is cooled to 70 ℃ to obtain deoxidized coal bed gas;
the composition of the deoxidized coal bed gas at the outlet of the water scrubber 5 is as follows: 3.59% of methane, 1.13% of hydrogen, 11.28% of carbon dioxide, 0.28% of oxygen, 51.80% of nitrogen, 4.68% of carbon monoxide, 26.62% of water gas and 0.62% of inert gas. The methane loss rate was 1.44%.
Example 2
a. The raw material gas composition (volume) is as follows: methane 14.88%, nitrogen 66.46%, oxygen 17.83%, inert gas 0.83%, pressure 8kPa (gauge pressure), raw material gas enters saturation tower 1 of saturation tower 1, enters saturation tower 1 with water temperature of 80 ℃, and composition (volume) of raw material gas at outlet of saturation tower 1 is: 9.72% of methane, 43.41% of nitrogen, 11.65% of oxygen, 34.69% of water gas and 0.53% of inert gas;
b. the outlet gas of the saturation tower 1 enters a tubular reactor 2, and the space velocity in the tubular reactor 2 is 2500h -1 The temperature of a reaction bed layer is 600 ℃, and the granularity of the semi-coke lignite is 3-5 mm;
c. gas at the outlet of the tubular reactor 2 enters a cooler 4, is cooled to 160 ℃, and then is introduced into a washing tower 5 and is cooled to 77 ℃ to obtain deoxidized coal bed gas;
the composition of the deoxidized coal bed gas at the outlet of the water scrubber 5 is as follows: 8.89% of methane, 1.53% of hydrogen, 8.84% of carbon dioxide, 0.19% of oxygen, 40.39% of nitrogen, 3.61% of carbon monoxide, 36.06% of water vapor and 0.49% of inert gas. The methane loss rate was 1.69%.
Example 3
a. The raw material gas composition (volume) is as follows: 8.77% of methane, 71.23% of nitrogen, 19.11% of oxygen and 0.89% of inert gas, wherein the flow rate of the raw material gas is 20Nm 3 The pressure is 5kPa (gauge pressure), the raw material gas enters the saturation tower 1, the water temperature of the saturation tower 1 is 77 ℃, and the composition (volume) of the gas at the outlet of the saturation tower 1 is as follows: 5.45% of methane, 44.27% of nitrogen, 11.88% of oxygen, 37.87% of water vapor and 0.53% of inert gas;
b. the outlet gas of the saturation tower 1 enters a tubular reactor 2, and the space velocity of the gas in the tubular reactor 2 is 1000h -1 The bed temperature of the reactor is 530 ℃, and the granularity of the semi-coke is 3-5 mm;
c. gas at the outlet of the tubular reactor 2 enters a cooler 4, is cooled to 160 ℃, and then is introduced into a washing tower 5, and is cooled to 78 ℃ to obtain deoxidized coal bed gas;
the composition of the deoxidized coal bed gas at the outlet of the water scrubber 5 is as follows: 5.08% of methane, 1.34% of hydrogen, 9.04% of carbon dioxide, 0.28% of oxygen, 42.03% of nitrogen, 3.91% of carbon monoxide, 37.81% of water vapor and 0.51% of inert gas. The methane loss rate was 1.77%.
Example 4
a. The raw material gas composition (volume) is as follows: 7.49% of methane, 72.23% of nitrogen, 19.38% of oxygen and 0.87% of inert gas, wherein the pressure is 5kPa (gauge pressure), the raw material gas enters the saturation tower 1, the water temperature of the raw material gas enters the saturation tower 1 is 75 ℃, and the composition (volume) of the gas at the outlet of the saturation tower 1 is as follows: 4.25% of methane, 40.99% of nitrogen, 11.00% of oxygen, 43.27% of water gas and 0.49% of inert gas;
b. the gas at the outlet of the saturation tower 1 enters a tubular reactor 2, and the gas space velocity in the tubular reactor 2 is 2000h -1 The bed temperature of the reactor is 660 ℃, and the particle size of the coke is 3-5 mm;
c. gas at the outlet of the tubular reactor 2 enters a cooler 4, is cooled to 200 ℃, and then is introduced into a washing tower 5 and is cooled to 70 ℃ to obtain deoxidized coal bed gas;
the composition of the deoxidized coal bed gas at the outlet of the water scrubber 5 is as follows: 3.93% of methane, 1.26% of hydrogen, 7.64% of carbon dioxide, 0.31% of oxygen, 38.63% of nitrogen, 4.83% of carbon monoxide, 42.93% of water vapor and 0.47% of inert gas. The methane loss rate was 1.88%.
Comparative example 1
The process of example 2 was followed except that in step b, the temperature of the reaction bed in the tubular reactor 2 was increased from 600 ℃ to 750 ℃; the rest of the implementation method is the same as the embodiment 2;
the composition of the deoxidized coal bed gas at the outlet of the water washing tower is as follows: 7.87% of methane, 1.61% of hydrogen, 7.78% of carbon dioxide, 0.05% of oxygen, 38.67% of nitrogen, 5.89% of carbon monoxide, 38.63% of water vapor and 0.47% of inert gas. The methane loss rate was 10.21%. The results are shown in Table 1.
Comparative example 2
The process of example 2 was followed except that in step b, the temperature of the reaction bed in the tubular reactor 2 was reduced from 600 ℃ to 400 ℃; the rest of the implementation method is the same as the embodiment 2;
the deoxidation coal bed gas at the outlet of the washing tower comprises the following components: 8.65% of methane, 0.26% of hydrogen, 6.27% of carbon dioxide, 1.16% of oxygen, 38.67% of nitrogen, 5.89% of carbon monoxide, 38.63% of water vapor, 0.47% of inert gas and 0.05% of methane loss rate.
The results are shown in Table 1.
TABLE 1 deoxidation results for coalbed methane examples 1-4 and comparative examples 1-2
It can be seen from the results of examples 1 to 4 in table 1 that, by adopting the steps of the present invention, the methane concentration and/or the oxygen concentration in the coal bed gas can be adjusted to be outside the explosion limit by adding water vapor, so as to ensure the safety of the deoxidation process of the coal bed gas; and the loss rate of methane in the deoxidation process of the coal bed gas is less than 5 percent.
As can be seen from comparative example 1 in Table 1, too high a deoxygenation temperature results in substantial cracking of methane in the coal seam gas, resulting in a higher methane loss rate. As can be seen from comparative example 2 in Table 1, the deoxidation temperature was too low, resulting in incomplete deoxidation. The deoxidation method provided by the invention can be used for effectively controlling the deoxidation degree and the methane loss rate.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A deoxidation method for low-concentration coal bed gas is characterized by comprising the following steps:
(1) contacting the coal bed gas with hot water to obtain a material I; the content of the coal bed methane is 5-16%, and the content of the oxygen is 14-20%; the oxygen content of the material I is less than or equal to 12 percent, and/or the methane content is less than or equal to 4 percent;
(2) performing deoxidation reaction on the material I and a carbon material to obtain a material II; the deoxidation reaction temperature is 500-700 ℃; the oxygen content of the material II is less than or equal to 0.5 percent;
(3) cooling the material II to 130-250 ℃, washing and dedusting, and then cooling to 50-85 ℃ to obtain deoxidized coal bed gas;
wherein, the gas content is based on the volume content.
2. The deoxidation method of claim 1 wherein in step (1) the coal bed gas pressure is 3 to 10kPa (gauge) and the hot water temperature is 50 to 85 ℃.
3. The deoxidation method according to claim 1 or 2, wherein, in step (2), the deoxidation reaction conditions comprise: the temperature is 525 ℃ plus 700 ℃, and the gas space velocity is 1000h plus 3000h -1 (ii) a The carbon material is at least one of semi-coking coal, anthracite, semi-coke, coke and biochar;
preferably, the carbon material particle size is 3-5 mm.
4. A low-concentration coal bed gas deoxidation method is characterized in that the method is carried out in a system comprising a saturation tower (1), a tubular reactor (2), a steam drum (3), a cooler (4) and a washing tower (5), and the method comprises the following steps:
a. the coal bed gas is in countercurrent contact with hot water in a saturation tower (1) to obtain a material I; based on the volume content, the content of the coal bed methane is 5-16%, and the content of the oxygen is 14-20%; the oxygen content of the material I is less than or equal to 12%, and/or the methane content is less than or equal to 4%;
b. the material I enters a tubular reactor (2) and is subjected to deoxidation reaction with a carbon material to obtain a material II; the deoxidation reaction temperature is 500-700 ℃; the oxygen content of the material II is less than or equal to 0.5 percent;
the boiler water of the tubular reactor (2) is gasified, the generated steam is sent to a steam drum (3), after steam-water separation is carried out on the steam drum (3), steam and saturated water are obtained, and the saturated water is sent back to the tubular reactor (2);
c. cooling the material II to the temperature of 130-250 ℃ in the cooler (4), washing and dedusting in the washing tower (5), and cooling to the temperature of 50-80 ℃ to obtain deoxidized coal bed gas; wherein, the gas content is based on the volume content; .
5. The deoxidation method of claim 4, wherein in step a, the coal bed gas pressure is 3-10kPa (gauge) and the hot water temperature is 50-85 ℃.
6. The deoxidation method according to claim 4, wherein in step b, the deoxidation reaction conditions of the material I and the carbon material in the shell-and-tube reactor (2) comprise: the temperature is 525 ℃ plus 700 ℃, and the gas space velocity is 1000h plus 3000h -1 (ii) a The carbon material is at least one of semi-coking coal, anthracite, semi-coke, coke and biochar; preferably, the carbon material particle size is 3-5 mm.
7. Deoxygenation method according to any of the claims 4-6, wherein the reaction temperature of the shell and tube reactor (2) is controlled by the boiler water of the cooler (4).
8. The deoxidation method of claim 7 wherein the boiler water temperature is 45-55 ℃.
9. The method according to any one of claims 4 to 8, wherein the washing tower (5) is used for washing and dedusting by countercurrent contact of cooling water and/or supplementary cooling water at the bottom of the saturation tower (1) and the material II from the cooler (4); the temperature of the cooling water and/or the supplementary cooling water at the bottom of the saturation tower (1) is 25-35 ℃.
10. A low-concentration coal bed gas deoxidation system is characterized by comprising:
the system comprises a saturation tower (1), a tubular reactor (2), a steam drum (3), a cooler (4) and a washing tower (5);
wherein the saturation tower (1) is used for carrying out countercurrent contact on coal bed gas and hot water in the saturation tower to obtain a material I;
wherein the tubular reactor (2) is used for performing deoxidation reaction on the material I and the carbon material in the tubular reactor to obtain a material II;
wherein the cooler (4) is used for cooling the material II in the cooler;
wherein the washing tower (5) is used for washing and dedusting the cooled materials to obtain the deoxidized coal bed gas;
cold water and/or supplementary cooling water discharged from the bottom of the saturation tower (1) are/is sent to a washing tower (5) to be used as cooling water, and hot water discharged from the bottom of the washing tower (5) is sent to the saturation tower (1) to be used as spray water;
the cooler (4) is connected with the tubular reactor (2) through a pipeline, so that boiler water in the cooler (4) can be conveyed to the tubular reactor, and the temperature of the tubular reactor (2) is controlled by the boiler water;
the boiler water of the tubular reactor (2) is gasified, the generated steam is sent to the steam drum (3), after the steam-water separation of the steam drum (3), steam and saturated water are obtained, and the saturated water is sent back to the tubular reactor (2).
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